JPH11310713A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which can give a molding having excellent antistatic properties, excellent water resistance and mechanical strengths, especially, impact strength and good surface properties such as appearance. SOLUTION: This composition comprises 1-50 pts.wt. modifier (A) comprising a high-molecular-weight alkylene oxide polymer (a), a low-molecular-weight alkylene oxide polymer (b), and a metal salt (c) and 100 pts.wt. thermoplastic resin (B). In modifier A, the rate of component (b) is 5-50 wt.% based on component (a), and the rate of component (c) is 0.3-10 wt.% based on the total amount of components (a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having excellent antistatic properties and mechanical strength, and more particularly to a thermoplastic resin composition which gives a molded article having excellent impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins are easy to mold and process.
In addition, molded products have excellent properties and economic advantages, so that they are widely used in various applications. In particular, thermoplastic resins are used for many electrical components as electrical insulators because of their excellent electrical insulation properties.However, this is because on the other hand, molded products tend to be charged, and dust tends to adhere and become dirty. Cause problems. As a means for preventing the above problem, there is a method of imparting an antistatic property to a thermoplastic resin.

[0003] As a method of imparting an antistatic property to a thermoplastic resin, a method of applying an antistatic agent to a surface, adding an antistatic agent to a resin, and kneading the resin has conventionally been used. Particularly, in order to provide an antistatic effect for a long period of time, it has been proposed to add a high molecular weight antistatic agent to a thermoplastic resin. For example, Japanese Patent Application Laid-Open No. 64-26674 discloses a method of blending an ethylene oxide copolymer having a molecular weight of 20,000 or more, and Japanese Patent Application Laid-Open No. 6-200171 discloses an alkylene oxide having a molecular weight of 20,000 to 10 million containing ethylene oxide as one component. A method of mixing a copolymer and a metal salt has been proposed.

[0004]

However, in these methods, the high molecular weight ethylene oxide copolymer used as an antistatic agent has a high melt viscosity and a large difference in viscosity from a thermoplastic resin. Difficult to disperse in resin. Also, when molding a thermoplastic resin to which an antistatic agent is added, even in the case of high-shear molding such as injection molding, since the antistatic agent hardly concentrates on the surface layer, a relatively large amount of the antistatic agent must be added. Must. For this reason, the resulting molded article may have a deteriorated mechanical property, or may have an impaired appearance due to delamination or the like.

The present invention provides a thermoplastic resin composition which has excellent antistatic properties, and is excellent in water resistance and mechanical strength, particularly excellent in impact strength, and which gives a molded article having a good surface condition such as appearance. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventor has found that a high molecular weight alkylene oxide polymer, a low molecular weight alkylene oxide polymer and a specific metal salt are added to a thermoplastic resin. Addition of a three-component modifier gives thermoplastics with excellent antistatic properties and excellent molded article with excellent water resistance and mechanical strength, especially excellent impact resistance, and good surface condition such as appearance. The present inventors have found that a resin composition can be obtained, and have completed the present invention.

That is, the thermoplastic resin composition of the present invention comprises:
1 to 50 parts by weight of a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c), and 100 parts by weight of a thermoplastic resin (B) Wherein the proportion of the component (b) in the modifier (A) is 5 to 50% by weight based on the component (a).
Wherein the proportion of the component (c) in the modifier (A) is 0.3 to 10% by weight based on the total amount of the components (a) and (b).

In the present invention, the use of a modifier (A) in which a low molecular weight alkylene oxide polymer (b) is added as a third component to a high molecular weight alkylene oxide polymer (a) and a metal salt (c) is used. The biggest feature. The addition of the low molecular weight alkylene oxide polymer (b) lowers the melt viscosity of the modifier (A), so that the modifier (A) can be finely dispersed in the thermoplastic resin (B) even at a relatively low shear kneading. A uniformly dispersed thermoplastic resin composition is obtained.
Further, when the thermoplastic resin composition is molded, under high shear such as injection molding, the modifier (A) is concentrated on the surface layer of the molded product, and further forms a streak-like structure. Even if the modifier (A) is added, a molded article having excellent antistatic properties, excellent water resistance and mechanical strength, particularly excellent impact resistance, and good surface condition such as appearance can be obtained. Conceivable.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, the modifier (A) in the present invention comprises a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c).

Among them, the high molecular weight alkylene oxide polymer (a) has a weight average molecular weight of 200,000 to 100
A high molecular weight alkylene oxide homopolymer and / or a high molecular weight alkylene oxide copolymer having a molecular weight of 100,000, preferably 500,000 to 6,000,000 are exemplified. Weight average molecular weight 2
If it is less than 10,000, it is difficult to obtain a continuous antistatic effect. When the weight average molecular weight exceeds 10,000,000, the high molecular weight alkylene oxide polymer (a) becomes difficult to knead with other components of the modifier, and the surface state of the molded article tends to be deteriorated.

Examples of the high molecular weight alkylene oxide homopolymer include polyethylene oxide, polypropylene oxide and the like. In particular, the weight average molecular weight is from 200,000 to 1,000,000.
Ten million polyethylene oxides are preferably used.

The high molecular weight alkylene oxide copolymer is preferably an alkylene oxide copolymer containing ethylene oxide as one component. Components other than ethylene oxide in the high molecular weight alkylene oxide copolymer include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and the like. Among them, propylene oxide is preferred. The high molecular weight alkylene oxide copolymer can be produced by copolymerizing ethylene oxide with another copolymerizable alkylene oxide in the presence of a suitable alkali, metal catalyst or the like. The production method is not particularly limited, and a known method such as the method described in JP-A-5-17566 can be used.

Although there is no particular limitation on the composition ratio of ethylene oxide and other alkylene oxides in the high molecular weight alkylene oxide copolymer, the molar composition ratio of ethylene oxide contained in the high molecular weight alkylene oxide copolymer is as follows. The content is preferably 60 to 99% based on the whole copolymer. When the molar composition ratio is within the above range, the crystallinity of the copolymer can be reduced, the compatibility with the resin is improved, and it is premised that the low molecular weight alkylene oxide polymer (b) coexists. However, a resin composition having excellent antistatic properties can be obtained. If the molar composition ratio of ethylene oxide is less than 60%, a sufficient antistatic effect may not be obtained.

On the other hand, the low molecular weight alkylene oxide polymer (b) has a weight average molecular weight of 5,000 to 2,000.
0, preferably 10,000 to 15000 low molecular weight alkylene oxide homopolymer and / or low molecular weight alkylene oxide copolymer. When the weight average molecular weight is less than 5000, the low molecular weight alkylene oxide polymer (b) such as seepage to the surface is easily eluted,
There is a possibility that the surface condition of the molded product may be deteriorated. When the weight average molecular weight is more than 20,000, the effect of lowering the melt viscosity of the modifier may not be sufficiently obtained.

The low molecular weight alkylene oxide homopolymer includes polyethylene oxide, polypropylene oxide and the like, and especially has a weight average molecular weight of 5,000 to 5,000.
20000 polyethylene oxide is preferred.

As the low molecular weight alkylene oxide copolymer, an alkylene oxide copolymer containing ethylene oxide as a component is preferable. As components other than ethylene oxide of the low molecular weight alkylene oxide copolymer,
Examples include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and the like. Among them, propylene oxide is preferred. The low molecular weight alkylene oxide copolymer can be produced by copolymerizing ethylene oxide with another copolymerizable alkylene oxide in the presence of a suitable alkali, metal catalyst or the like. The production method is not particularly limited, and a known method can be used.

Although there is no particular limitation on the composition ratio of ethylene oxide and other alkylene oxides in the low molecular weight alkylene oxide copolymer, the molar composition ratio of ethylene oxide contained in the low molecular weight alkylene oxide copolymer depends on the copolymerization ratio. It is preferable that the content is 60 to 99% based on the whole united body. When the molar composition ratio is within the above range, the crystallinity of the copolymer can be reduced, the compatibility with the resin is improved, and a resin composition having excellent antistatic properties can be obtained. The molar composition ratio of ethylene oxide is 6
If it is less than 0%, a sufficient antistatic effect may not be obtained.

The metal salt (c) used in the present invention is preferably a metal salt having an alkali metal or an alkaline earth metal. Specifically, the metal salt (c) is represented by the following formula (1): MX _n (1) And a metal salt of an organic sulfonic acid represented by the following formula (2) (R-SO ₃ ) _n M (2). Here, M in the formula (1) represents an alkali metal or an alkaline earth metal, and X represents a halogen atom, SCN, C
10 ₄ , BF ₄ , PF ₆ , B [Ph] ₄ (however, Ph
Represents a phenyl group), CF ₃ SO ₃ , or CF ₃ C
Represents O ₂ , and n represents 1 or 2. R in the formula (2) represents an alkyl group or an alkylphenyl group, M represents an alkali metal or an alkaline earth metal,
n represents 1 or 2.

The ion dissociable metal salt represented by the formula (1) has an alkali metal such as lithium, potassium, and sodium, or an alkaline earth metal such as magnesium and calcium, and has a fluorine ion (F ⁻ ), chlorine ion (Cl ^-), bromine ion (Br ^-), iodide ion (I
^-), thiocyanate ion (SCN ^-), perchlorate ion (ClO ₄ ^-), tetrafluoroborate ion (BF
₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), tetraphenylborate ion (B [Ph] ₄ ⁻ ), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ ), or trifluoroacetic acid ion (CF ₃ ⁻ ). CO ₂ ^-) to liberate.

The metal salt of an organic sulfonic acid represented by the formula (2) is preferably a metal salt of a sulfonic acid having a straight-chain or branched alkyl group or an alkylphenyl group having 1 to 30 carbon atoms, for example, methyl, octyl, dodecyl. , Stearyl, behenyl and the like, and alkyl phenyl sulfonic acid such as dodecylbenzene. The metal constituting the metal salt can be arbitrarily selected from alkali metals such as lithium, potassium and sodium, and alkaline earth metals such as magnesium and calcium.

The metal salt represented by the formula (1) or (2) may be used alone or as a mixture of two or more. In addition to the metal salt represented by the formula (1) or (2), a metal carboxylate such as lithium acetate, sodium propionate, and potassium stearate can also be used.

In the modifier (A) comprising the high molecular weight alkylene oxide polymer (a), the low molecular weight alkylene oxide polymer (b) and the metal salt (c), the component (b)
Is 5 to 50% by weight, preferably 10 to 40% by weight, based on the component (a). If the ratio of the component (b) to the component (a) is less than 5% by weight, a sufficient antistatic effect cannot be obtained. The ratio of component (b) to component (a) is 50
If the content is more than 10% by weight, processability as a modifier may be deteriorated, or when a thermoplastic resin composition is molded, bleeding to the surface may occur, and the surface condition of the molded product may be deteriorated.

In the modifier (A), the ratio of the component (c) is 0.3% with respect to the total amount of the components (a) and (b).
10 to 10% by weight, preferably 1 to 5% by weight. If the ratio of the component (c) to the total amount of the components (a) and (b) is less than 0.3% by weight, a sufficient antistatic effect cannot be obtained. When the proportion of the component (c) exceeds 10% by weight,
The effect of adding a large amount of component (c) cannot be obtained, which is economically disadvantageous.

The thermoplastic resin (B) used in the present invention is not particularly limited, and a general thermoplastic resin can be used. For example, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin)
Styrene resins such as polyethylene, polypropylene, etc., polymethacrylate resins such as polymethyl methacrylate and polyethyl methacrylate, vinyl acetate resins, vinyl alcohol resins, and vinyl chloride resins. Resins, fluorine-containing resins, polyester resins such as polybutylene terephthalate, polyethylene terephthalate, ether-ester copolymers, polyurethane resins, polyamide resins, polycarbonate resins, and polyacetal resins. . In the present invention, styrene resins such as polystyrene, acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin) are particularly preferably used. These thermoplastic resins may be used alone or as a mixture of two or more.

In the thermoplastic resin composition of the present invention,
1 to 50 parts by weight of the modifier (A) is added to 100 parts by weight of the thermoplastic resin (B). If the amount of the modifier (A) is less than 1 part by weight, a sufficient antistatic effect cannot be obtained. When the amount of the modifier (A) exceeds 50 parts by weight,
The inherent properties of the thermoplastic resin, such as a decrease in the mechanical strength of the molded product and a deterioration in the surface condition, are impaired.

The method for producing the thermoplastic resin composition of the present invention will be described. In addition, what is related to the manufacturing method of a thermoplastic resin composition, such as a kneading machine, a kneading method, and a timing of adding a compounding component, is not particularly limited. Hereinafter, an example of the manufacturing method will be described.

First, a single screw extruder, a twin screw extruder, a kneader,
The high molecular weight alkylene oxide polymer (a), the low molecular weight alkylene oxide polymer (b) and the metal salt (c) are mixed at a predetermined ratio by a twin-screw kneader or the like. 7
What was kneaded and pelletized in a temperature range of 0 to 120 ° C is referred to as a modifier (A). Next, a single screw extruder, a twin screw extruder,
Using a kneader, a twin-screw kneader or the like, the modifier (A) and the thermoplastic resin (B) are kneaded at a predetermined ratio in a temperature range of 130 to 270 ° C. to obtain a thermoplastic resin composition. By usual methods such as injection molding, compression molding, blow molding, extrusion molding,
A molded article is manufactured from the obtained thermoplastic resin composition.

To the thermoplastic resin composition of the present invention, a plasticizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a slipper, a pigment, a reinforcing agent and the like are added in such an amount that the antistatic property is not impaired. You can also. If there are other components to be added,
It is possible to add an appropriate amount according to the purpose of addition.

[0030]

Next, the thermoplastic resin composition of the present invention will be described more specifically with reference to examples and comparative examples. In the Examples and Comparative Examples, the components described below and the methods for obtaining the same and the methods for measuring the physical properties of the obtained resin compositions were employed. The abbreviations (alphabet) described in [] are as described below, and are shown in Table 1 as they are.

1. Components of modifier (A) (a) High molecular weight alkylene oxide polymer Obtaining method: Using an organozinc compound-alcohol catalyst, changing the charged amounts of ethylene oxide and propylene oxide, the molar composition ratio of ethylene oxide and propylene oxide The following four types of alkylene oxide copolymers having different The composition ratio of each high molecular weight alkylene oxide polymer (a) was analyzed by a nuclear magnetic resonance spectrum. [A]: Polyethylene oxide weight average molecular weight 2,000,000 [B]: Ethylene oxide (90%)-propylene oxide (10%) copolymer weight average molecular weight 2,000,000 [C]: Ethylene oxide (80%)-propylene oxide (20% ) Copolymer Weight average molecular weight 2,000,000 [D]: Ethylene oxide (80%)-propylene oxide (20%) copolymer Weight average molecular weight 4,000,000

(B) Low molecular weight alkylene oxide polymer [L]: polyethylene oxide (PEG15000: manufactured by Kanto Chemical Co., Ltd.) Weight average molecular weight 15000 [M]: ethylene oxide (80%)-propylene oxide (20%) copolymer Combined (Epan U-180: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Weight average molecular weight 13000 [N]: Ethylene oxide (75%)-propylene oxide (25%) copolymer (Yukon 75H: manufactured by Union Carbide) Weight Average molecular weight 15,000

(C) Metal salt [X]: NaSCN (sodium thiocyanate) [W]: Sodium dodecylbenzenesulfonate

2. Thermoplastic resin (B) [ABS]: ABS resin (Toyolac 500: manufactured by Toray Industries, Inc.) [PP]: Polypropylene resin (Noblen H501:
(Sumitomo Chemical Co., Ltd.)

3. Method for measuring physical properties of molded resin composition (1) Surface resistivity (unit: Ω) A resin composition is injection-molded to have a diameter of 10 cm and a thickness of 0.2 c.
Two m-shaped disc-shaped test pieces were produced. One of them is kept at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours,
The test piece before washing was used. Apart from the test piece, the remaining 1
Each test piece was immersed in pure water for 15 minutes. Thereafter, the surface of the test piece was washed with pure water, and then the temperature was 23 ° C. and the relative humidity was 50.
% In an atmosphere of 24% for use as a test piece after washing. The surface resistivity of both specimens was 23 ° C,
It was measured under the condition of a relative humidity of 50%, and evaluated as antistatic property before and after washing. The surface specific resistance is measured using a super-insulation meter (S
M-8210: manufactured by Toa Denpa Kogyo Co., Ltd.) under the conditions of a measurement voltage of 100 V and an application time of 1 minute.

(2) Izod impact strength (unit: kJ /
m) Izod impact strength was measured using an impact tester (manufactured by Toyo Seiki Co., Ltd.) according to JIS K7110.

(3) Surface Condition The appearance of the molded product was visually observed and evaluated according to the following criteria. ：: Good surface state without delamination of the surface or stickiness. X: Layered peeling is observed on the surface or sticky.

Example 1 Ethylene oxide (80%) having a weight average molecular weight of 2,000,000-propylene oxide (20%)
%) Copolymer 10 weight parts, ethylene oxide (80%) having a weight average molecular weight of 13,000-propylene oxide (2%).
0%) 1 part by weight of a copolymer (Epan U-180: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.3 part by weight of sodium thiocyanate, and an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) 100 parts to 120 ° C. of 1 part by weight using an electrically heated two-roll kneader (TM type: manufactured by Yasuda Seiki)
After kneading for 10 to 20 minutes, the mixture was pelletized to obtain a modifier. Next, ABS resin (Toyolac 500: Toray Industries, Inc.)
100 parts by weight) and 11.4 parts by weight of the above modifier, and then mixed with a twin-screw extruder (30 mm in diameter).
After melting and kneading at ~ 240 ° C, the mixture was pelletized, and this pellet was used as the thermoplastic resin composition of the present invention. After the obtained pellets were completely dried in a hot air circulating oven at 75 to 80 ° C. for 6 hours or more, the cylinder temperature was 200 to 230 using an injection molding machine (manufactured by Nippon Steel Works, Ltd.).
C. and a mold temperature of 40 ° C., and test pieces corresponding to each test method were prepared. Each physical property was evaluated using these test pieces. Table 1 shows the obtained results.

Example 2 Ethylene oxide (80%) having a weight average molecular weight of 13,000 used in Example 1
Propylene oxide (20%) copolymer (Epan U-1)
80: Daiichi Kogyo Seiyaku Co., Ltd.) 1 part by weight of ethylene oxide (75%) having a weight average molecular weight of 15,000
Propylene oxide (25%) copolymer (Yukon 75
H: manufactured by Union Carbide). The other conditions were the same as in Example 1 to prepare a modifier. Next, ABS resin (Toyolak 500: manufactured by Toray Industries, Inc.) 10
After mixing 0 parts by weight and 12.4 parts by weight of the modifier,
In the same manner as in Example 1, a thermoplastic resin composition of the present invention was obtained. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 3 Using the modifier of Example 2,
The amount of the modifier mixed with the ABS resin was changed to 24.8 parts by weight. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 4 Using the modifier of Example 2,
The amount of the modifier mixed with the ABS resin was changed to 6.2 parts by weight. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 5 In place of sodium thiocyanate used in Example 2, sodium dodecylbenzenesulfonate was used. Other conditions were used in Example 2.
And a thermoplastic resin composition of the present invention was obtained. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 6 In place of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 used in Example 2, ethylene oxide (80%) having a weight average molecular weight of 4,000,000 was used. %)-Propylene oxide (20%) copolymer was used. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 7 In place of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 used in Example 2, ethylene oxide (90%) having a weight average molecular weight of 2,000,000 was used. %)-Propylene oxide (10%) copolymer was used. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 8 Instead of the ethylene oxide (80%)-propylene oxide (20%) copolymer having a weight average molecular weight of 2,000,000 used in Example 2, polyethylene oxide having a weight average molecular weight of 2,000,000 was used. Using. Further, the weight average molecular weight used in Example 2 was 1500
0 ethylene oxide (75%)-propylene oxide (25%) copolymer (Yukon 75H: manufactured by Union Carbide) instead of polyethylene oxide having a weight average molecular weight of 15,000 (PEG15000, Kanto Chemical Co., Ltd.)
Was used. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

[Embodiment 9] AB used in Embodiment 4
Instead of S resin (Toyolac 500: manufactured by Toray Industries, Inc.),
A polypropylene resin (Noblen H501: manufactured by Sumitomo Chemical Co., Ltd.) was used. Other conditions were the same as in Example 4, to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Example 10 A used in Example 2
Instead of BS resin (Toyolac 500: manufactured by Toray Industries, Inc.), polypropylene resin (Nobren H501: manufactured by Sumitomo Chemical Co., Ltd.) was used. The other conditions were the same as in Example 2 to obtain a thermoplastic resin composition of the present invention. Test pieces were prepared from this thermoplastic resin composition in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 using an ABS resin (Toyolac 500: manufactured by Toray Industries, Inc.) to which no modifier was added, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 2 Ethylene oxide (80%) having a weight average molecular weight of 2,000,000-propylene oxide (20%)
%) Copolymer 10 parts by weight, ethylene oxide (75%)-propylene oxide (2
5%) 2 parts by weight of a copolymer (Yukon 75H: manufactured by Union Carbide) and an antioxidant (Sumilyzer BH
T: manufactured by Sumitomo Chemical Co., Ltd.) 0.1 parts by weight using an electric heating type two-roll kneader (TM type: manufactured by Yasuda Seiki)
After kneading at ~ 120 ° C for 10-20 minutes, it was pelletized to obtain a modifier. Next, ABS resin (Toyolac 500:
After mixing 100 parts by weight of Toray Industries, Inc. and 12.1 parts by weight of the modifier, the mixture was melted at 180 to 240 ° C. using a twin-screw extruder (30 mm in diameter), kneaded, and then pelletized. The pellet was used as a thermoplastic resin composition. After the obtained pellets were completely dried in a hot air circulating oven at 75 to 80 ° C. for 6 hours or more, the cylinder temperature was 200 to 230 using an injection molding machine (manufactured by Nippon Steel Works, Ltd.).
C. and a mold temperature of 40 ° C., and test pieces corresponding to each test method were prepared. Each physical property was evaluated using these test pieces. Table 1 shows the obtained results.

Comparative Example 3 Ethylene oxide (80%) having a weight average molecular weight of 2,000,000-propylene oxide (20%)
%) Copolymer 10 parts by weight, sodium thiocyanate 0.1%
3 parts by weight and 0.1 parts by weight of an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) were added to an electric heating type two-roll kneader (TM type: manufactured by Yasuda Seiki) for 100 to 12 parts.
After kneading at 0 ° C. for 10 to 20 minutes, the mixture was pelletized to obtain a modifier. Next, after mixing 100 parts by weight of an ABS resin (Toyolac 500: manufactured by Toray Industries, Inc.) and 10.4 parts by weight of the modifier, a test piece was prepared in the same manner as in Comparative Example 2 to evaluate each property. went. Table 1 shows the obtained results.

Comparative Example 4 Ethylene oxide (75%) having a weight average molecular weight of 15,000-propylene oxide (2
5%) 10 parts by weight of copolymer (Yukon 75H: manufactured by Union Carbide), 0.3 part by weight of sodium thiocyanate, antioxidant (Sumilyzer BHT: Sumitomo Chemical Co., Ltd.)
0.1 parts by weight and ABS resin (Toyolac 50
After mixing 100 parts by weight (0: manufactured by Toray Industries, Inc.), test pieces were prepared in the same manner as in Comparative Example 2 and each physical property was evaluated.
Table 1 shows the obtained results.

Comparative Example 5 Ethylene oxide (80%) having a weight average molecular weight of 2,000,000-propylene oxide (20%)
%) Copolymer 50 parts by weight, ethylene oxide (75%)-propylene oxide (2
5%) Copolymer (Yukon 75H: manufactured by Union Carbide) 20 parts by weight, sodium thiocyanate 2 parts by weight, and antioxidant (Sumilyzer BHT: Sumitomo Chemical Co., Ltd.)
0.7 parts by weight of electric heating type two-roll kneader (TM
(Type: manufactured by Yasuda Seiki)
After kneading for 20 minutes, it was pelletized to obtain a modifier. Next, ABS resin (Toyolak 500: manufactured by Toray Industries, Inc.) 10
After mixing 0 parts by weight and 72.7 parts by weight of the modifier,
A test piece was prepared in the same manner as in Comparative Example 2, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 6 Ethylene oxide (80%)-propylene oxide (20%) having a weight average molecular weight of 2,000,000
%) Copolymer 0.5 part by weight, weight average molecular weight 15,000
0.1 part by weight of ethylene oxide (75%)-propylene oxide (25%) copolymer (Yukon 75H: manufactured by Union Carbide), sodium thiocyanate 0.0
15 parts by weight, and an antioxidant (Sumilyzer BHT:
0.005 parts by weight of 1005 parts by weight using an electric heating type two-roll kneader (TM type: manufactured by Yasuda Seiki)
After kneading at ~ 120 ° C for 10-20 minutes, it was pelletized to obtain a modifier. Next, ABS resin (Toyolac 500:
After mixing 100 parts by weight of Toray Industries, Inc. and 0.62 parts by weight of the above modifier, a test piece was prepared in the same manner as in Comparative Example 2, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 7 Ethylene oxide (80%)-propylene oxide (20%) having a weight average molecular weight of 2,000,000
%) Copolymer 10 parts by weight, ethylene oxide (75%)-propylene oxide (2
5%) 12 parts by weight of a copolymer (Yukon 75H: manufactured by Union Carbide), 0.3 part by weight of sodium thiocyanate, and 0.2 part by weight of an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) The mixture was kneaded at 100 to 120 ° C. for 10 to 20 minutes using an electric heating type two-roll kneader (TM type: manufactured by Yasuda Seiki) and then pelletized to obtain a modifier. Next, ABS resin (Toyolac 500: Toray Industries, Inc.)
Manufactured) and 22.5 parts by weight of the modifier were mixed, and test pieces were prepared in the same manner as in Comparative Example 2 to evaluate each physical property. Table 1 shows the obtained results.

Comparative Example 8 Ethylene oxide (80%)-propylene oxide (20%) having a weight average molecular weight of 2,000,000
%) Copolymer 10 parts by weight, ethylene oxide (75%)-propylene oxide (2
5%) 0.2 parts by weight of copolymer (Yukon 75H: manufactured by Union Carbide), 0.3 parts by weight of sodium thiocyanate, and 0.1% by weight of antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) The part was kneaded at 100 to 120 ° C. for 10 to 20 minutes using an electrically heated two-roll kneader (TM type: manufactured by Yasuda Seiki) and then pelletized to obtain a modifier. Next, ABS resin (Toyolac 500: Toray Industries, Inc.)
Manufactured) and 10.6 parts by weight of the modifier were mixed, and test pieces were prepared in the same manner as in Comparative Example 2 to evaluate each physical property. Table 1 shows the obtained results.

Comparative Example 9 Polypropylene resin containing no modifier (Noblen H501: manufactured by Sumitomo Chemical Co., Ltd.)
, Test pieces were prepared in the same manner as in Example 1, and each physical property was evaluated. Table 1 shows the obtained results.

Comparative Example 10 Ethylene oxide (80%)-propylene oxide (2
0%) copolymer 10 parts by weight, sodium thiocyanate 0.3 part by weight, and an antioxidant (Sumilyzer BH
T: manufactured by Sumitomo Chemical Co., Ltd.) 0.1 parts by weight using an electric heating type two-roll kneader (TM type: manufactured by Yasuda Seiki)
After kneading at ~ 120 ° C for 10-20 minutes, it was pelletized to obtain a modifier. Next, after mixing 100 parts by weight of a polypropylene resin (Noblen H501: manufactured by Sumitomo Chemical Co., Ltd.) and 10.4 parts by weight of the above modifier, a test piece was prepared in the same manner as in Comparative Example 2 to obtain various physical properties. An evaluation was performed. Table 1 shows the obtained results.

[0058]

[Table 1]

As shown in Table 1, the test pieces obtained by molding the thermoplastic resin compositions of Examples 1 to 10 are excellent in surface specific resistance, impact strength and surface condition. On the other hand, the test piece of Comparative Example 2 in which no metal salt (c) was added or the test piece of Comparative Example 3 in which no low molecular weight alkylene oxide (b) was added at all had poor antistatic properties. Has become. In addition, the test piece of Comparative Example 4 to which no high-molecular-weight alkylene oxide (a) was added had a low impact strength, and the surface condition was further deteriorated. Therefore, by using the thermoplastic resin composition of the present invention,
It is clear that a molded article having excellent antistatic properties, excellent water resistance and mechanical strength, particularly excellent impact strength, and good surface condition such as appearance can be obtained.

[0060]

The thermoplastic resin composition of the present invention comprises a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c). Contains. The modifier (A) has better dispersibility in the thermoplastic resin (B) than the high molecular weight modifier not containing the low molecular weight alkylene oxide polymer (b), and is finely uniform with the thermoplastic resin (B). Mix with. As a result, a molded article obtained from the thermoplastic resin composition of the present invention, having only a small amount of the modifier (A) added, has excellent antistatic properties and a good surface state, and can be used for electronic parts and the like. It can be used with confidence in OA equipment and can be expected to have a wide range of applications.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinji Kato 1st Irifunecho, Shimarima-ku, Himeji-shi, Hyogo Sumitomo Seika Co., Ltd. (2) Inventor Kazuyuki Miura 1st Irifunecho, Shikarima-ku, Himeji-shi, Hyogo Sumitomo Seika Co., Ltd. 2nd Research Laboratory

Claims (12)

[Claims] 1. A thermoplastic resin (B) comprising 1 to 50 parts by weight of a modifier (A) comprising a high molecular weight alkylene oxide polymer (a), a low molecular weight alkylene oxide polymer (b) and a metal salt (c). ) 100 parts by weight, wherein the proportion of the component (b) in the modifier (A) is 5 to 50% by weight based on the component (a), and the component (b) in the modifier (A) A thermoplastic resin composition wherein the proportion of c) is 0.3 to 10% by weight based on the total amount of component (a) and component (b). 2. The thermoplastic resin composition according to claim 1, wherein the high molecular weight alkylene oxide polymer (a) has a weight average molecular weight of 200,000 to 10,000,000. 3. The thermoplastic resin composition according to claim 1, wherein the high molecular weight alkylene oxide polymer (a) is a high molecular weight alkylene oxide homopolymer and / or a high molecular weight alkylene oxide copolymer. 4. The thermoplastic resin composition according to claim 3, wherein the high molecular weight alkylene oxide homopolymer is polyethylene oxide. 5. The high molecular weight alkylene oxide copolymer is a copolymer containing ethylene oxide as one component, and the molar composition ratio of ethylene oxide contained in the copolymer is 60 to 99 relative to the whole copolymer. % Of the thermoplastic resin composition according to claim 3. 6. The thermoplastic resin composition according to claim 1, wherein the low molecular weight alkylene oxide polymer (b) has a weight average molecular weight of 5,000 to 20,000. 7. The low molecular weight alkylene oxide polymer (b) is a low molecular weight alkylene oxide homopolymer and / or a low molecular weight alkylene oxide copolymer. Thermoplastic resin composition. 8. The thermoplastic resin composition according to claim 7, wherein the low molecular weight alkylene oxide homopolymer is polyethylene oxide. 9. The low molecular weight alkylene oxide copolymer is a copolymer containing ethylene oxide as one component, and the molar composition ratio of ethylene oxide contained in the copolymer is 60 to 99 relative to the whole copolymer. % Of the thermoplastic resin composition according to claim 7. 10. The metal salt (c) is a metal salt having an alkali metal or an alkaline earth metal.
The thermoplastic resin composition according to any one of the above. 11. The metal salt (c) is represented by the following formula (1) MX _n (1) (wherein M represents an alkali metal or an alkaline earth metal, and X represents a halogen atom, SCN, ClO ₄ , BF ₄₎ , P
F ₆ , B [Ph] ₄ (where Ph is a phenyl group), C
An ion dissociable metal salt represented by F ₃ SO ₃ or CF ₃ CO ₂ , wherein n represents 1 or 2, or the following formula (2) (R—SO ₃ ) _n M (2) , R represents an alkyl group or an alkylphenyl group, M represents an alkali metal or an alkaline earth metal,
11. The thermoplastic resin composition according to claim 10, wherein n is 1 or 2. 12. The thermoplastic resin (B) is at least one selected from the group consisting of a polystyrene-based resin, a polyolefin-based resin, a polyvinyl chloride-based resin, and a polymethacrylate-based resin. The thermoplastic resin composition according to any one of the above.